The invention relates to new 1-arylpyrazoles and derivatives thereof which have some valuable properties either as pesticides or as intermediates to make other pesticides. The invention further pertains to compositions of said compounds and methods, using said compounds either as intermediates to make other pesticides, or for the control of pests particularly insects, in particular to the application of said compounds or compositions in agricultural methods of use or for animal protection, particularly as pesticides, for controlling arthropods.
International Patent Publication No. WO 87/03781 and European Patent Publication No. 295117, 154115, 201852 describe insecticidal 1-(substituted phenyl) pyrazoles. Other prior art is also found in the text of these patent applications or the patents issued therefrom.
International Patent Publications No. WO 93/06089 and WO 94/21606 also describe insecticidal 1(4xe2x80x94SF5 substituted phenyl) heterocycles which may be pyrroles as well as imidazoles or pyrazoles. The teaching of these patents is not substantially different from Iternational Patent Publication No. WO 87/03781 or from European Patent Publication No. 0295117 as far as pyrazoles are concerned.
It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.
Another object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole compounds against arthropods, especially insects, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health.
A third object of the present invention is to provide very active compounds with broad spectrum pesticidal activity, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, soil insecticidal, systemic, antifeeding or pesticidal activity via seed treatment.
A fourth object of the present invention is to provide compounds with substantially enhanced and more rapid activity, especially against insects and more particularly insects in their larval stages.
A fifth objective of the present invention is to provide compounds with greatly improved (faster and greater) penetration into pest species when topically applied and to thus provide enhanced movement of the compounds to the pesticidal site(s) of action within the pest.
These and other objectives of the invention are met in whole or part and shall become readily apparent from the description of the present invention which follows.
The invention thus relates to compounds having the general formula (I): 
wherein:
X is N or Cxe2x80x94R2;
Y is N or Cxe2x80x94R3;
W is N or Cxe2x80x94R4;
R2 and R3 are independently selected from H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO2, xe2x80x94S(O)nR8, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaninosulfonyl, and dialkylaminosulfonyl;
R4 is H, halogen, alkyl, alkoxy, CN, NO2, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, xe2x80x94CHxe2x95x90Nxe2x80x94OH, xe2x80x94CHxe2x95x90Nxe2x80x94O-alkyl, xe2x80x94S(NH2)(xe2x95x90NH), xe2x80x94S(O)nR8, mercapto, haloalkylcarbonyl, or a xe2x80x94Sxe2x80x94 radical so that two molecules are bound together to form a disulfide compound;
R5 is hydrogen, halogen, xe2x80x94NR9R10, xe2x80x94Nxe2x95x90CR11R19, xe2x80x94S(O)nR8, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl, haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl;
R8 is alkyl or haloalkyl, alkenyl or alkynyl, or a cycloalkyl ring containing 3 to 5 carbon atoms;
R11 is H, or alkyl;
R19 may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino, or R19 is phenyl, thienyl, pyridyl or furyl, each of which is unsubstituted or substituted with alkyl, haloalkyl, halogen, NO2, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;
R9 and R10 independent of one another, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; the alkyl portion of R9 and R10 may be substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, xe2x80x94C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, xe2x80x94CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is N or Cxe2x80x94R16;
n is zero, one or two;
R12, R13, R15, R16, are independently selected from hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
R22, R23,R24, R25, R26 are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF5, R8S(O)n; preferably R24 is halogen, haloalkyl or haloalkoxy; or R22 and R23 or R23 and R24 or R25 and R26 may also be together a divinylidene group (xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94) or a methylene diether (xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94) or halomethylene diether (xe2x80x94Oxe2x80x94CF2xe2x80x94Oxe2x80x94) so as to form a cyclic ring vicinal to the phenyl ring; or pesticidally acceptable salts thereof.
By the term xe2x80x9cpesticidally acceptable saltsxe2x80x9d is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts formed from compounds of formula (I) containing an amine group, include salts with inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for example acetates. Suitable salts with bases formed from compounds of formula (I) containing a suitably acidic group include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts.
In the present invention, some words are used in a specific sense:
The term xe2x80x9clower alkylxe2x80x94S(O)nxe2x80x9d means a radical of the formula xe2x80x94S(O)nxe2x80x94 lower alkyl. The term xe2x80x9cR10S(O)nxe2x80x9d means a radical of the formula xe2x80x94S(O)nR10. The term xe2x80x9caminocarbonylxe2x80x9d means a carbamoyl radical, that is, a radical of the formula xe2x80x94C(O)NH2. Similarly, the term xe2x80x9calkylaminocarbonylxe2x80x9d means an alkylcarbamoyl radical, that is, a radical of the formula xe2x80x94C(O)xe2x80x94NH-alkyl; and the term xe2x80x9cdialkylaminocarbonylxe2x80x9d means a dialkylcarbamoyl radical, that is, a radical of the formula xe2x80x94C(O)xe2x80x94N(alkyl)2 in which the alkyl moieties can be the same or different. The term xe2x80x9caminosulfonylxe2x80x9d means a sulfamoyl radical, that is, xe2x80x94SO2NH2. Similarly, the term xe2x80x9calkylaminosulfonylxe2x80x9d means an alkylsulfamoyl radical, that is, a radical of the formula xe2x80x94SO2NH-alkyl; while the term xe2x80x9cdialkylaminosulfonylxe2x80x9d means a dialkylsulfamoyl radical, which has the formula xe2x80x94SO2N(alkyl)2 wherein the alkyl moieties can be the same or different.
The term xe2x80x9chaloxe2x80x9d before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl. The term xe2x80x9chalogenxe2x80x9d means F, Cl, Br or I. The term xe2x80x9clowerxe2x80x9d before the name of a radical having a carbon skeleton means that this carbon skeleton has less than 6 carbon atoms. When the name of any substituent is repeated, it keeps the same meaning unless otherwise specified. The term xe2x80x9carylxe2x80x9d designates a carbon and/or heteroatom-containing aromatic radical which is preferably phenyl optionally substituted with one or more substituents selected from halogen, methyl and methoxy, especially phenyl, halophenyl, tolyl or xylyl. The term xe2x80x9caroylxe2x80x9d designates a carbonyl aromatic radical, that is, arylxe2x80x94C(O)xe2x80x94, which is preferably a benzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl radical. The term xe2x80x9cacylxe2x80x9d designates an alkylcarbonyl radical. The various individual radicals (such as alkyl, alkenyl, alkynyl, alkoxy and alkylene or the like) generally contain up to six carbon atoms.
A preferred class of compounds of formula (I) is that wherein
X is N;
Y is Cxe2x80x94R3;
W is Cxe2x80x94R4;
R3 is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO2, xe2x80x94S(O)nR8, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl;
R4 is H, halogen, alkyl, alkoxy, CN, NO2, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, xe2x80x94CHxe2x95x90Nxe2x80x94OH, xe2x80x94CHxe2x95x90Nxe2x80x94O-alkyl, xe2x80x94S(NH2)(xe2x95x90NH), xe2x80x94S(O)nR8, mercapto, haloalkylcarbonyl, or a xe2x80x94Sxe2x80x94 radical so that two molecules are bound together to form a disufide compound;
R5 is hydrogen, halogen, xe2x80x94NR9R10, xe2x80x94Nxe2x95x90CR11R19, xe2x80x94S(O)nR8, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, lower alkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, preferably, amino xe2x80x94NR9R10;
R8 is alkyl or haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R8 is lower alkyl;
R11 is H or alkyl;
R19 may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino;
or R19 is phenyl, thienyl, pyridyl or furyl, all of them being optionally substituted with alkyl, haloalkyl, halogen, NO2, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;
R9 and R10 are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8xe2x80x94S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; the alkyl portion of R9 and R10 may be substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, xe2x80x94C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, xe2x80x94CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is N or Cxe2x80x94R16;
n is zero, one or two;
R12, R13, R15, R16, are separately hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
R22, R23, R24, R25, R26 are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF5, R8S(O)n, preferably, R24 is halogen, haloalkyl or haloalkoxy; or R22 and R23 or R23 and R24 or R25 and R26 may also be together a divinylidene group (xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94) or a methylene diether (xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94) or halomethylene diether (xe2x80x94Oxe2x80x94CF2xe2x80x94Oxe2x80x94) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof.
Another preferred class of the compounds of formula (I) are those with one or more of the following features wherein:
X is N or Cxe2x80x94R2;
Y is N or Cxe2x80x94R3;
W is N or Cxe2x80x94R4;
R3 is CN or halogen;
R4 is H, halogen, formyl, or xe2x80x94S(O)nR8;
R5 is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, or xe2x80x94NR9R10;
R8 is methyl, ethyl, xe2x80x94CF3, xe2x80x94CFCl2, xe2x80x94CF2Cl;
R12 and R16 are independently selected from F, Cl, Br and H;
R13 and R15 are H;
R24 is xe2x80x94CF3, xe2x80x94OCF3, xe2x80x94CHF2, xe2x80x94S(O)nCF3, xe2x80x94CFCl2, xe2x80x94CF2Cl, xe2x80x94OCF2Cl, xe2x80x94OCFCl2, Cl, Br or F; or
Z is CCl, CF, CBr or N.
A further especially preferred class of compounds are those wherein:
X is N;
Y is Cxe2x80x94R3;
W is Cxe2x80x94R4;
R12 and R16 are Cl or Br;
R13 and R15 are H;
R24 is xe2x80x94CF3, xe2x80x94OCF3 or Br;
R5 is amino;
R9 and R10 are H, alkyl or alkylcarbonyl;
R8 is methyl or ethyl or CF3, CCl2F, CClF2; and
R3 is CN or halogen.
For the above preferred compounds, there are optimum combinations of substituent groups.
Further, preferred S(O)nR8 substituents in formula (I) are: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichloromethylsulfinyl, dichloromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
Some compounds are useful as intermediates to make other pesticides, others are useful directly as pesticides. Compounds wherein R23 or R24 or R25 is formyl are preferred as intermediates as well as compounds wherein R5 is H or compounds wherein simultaneously R4 is not halogenated and R22 and R23 and R24 and R25 and R26 are H.
The compounds of general formula (I) can be prepared by the application or adaptation of known methods (i.e., methods heretofore used or described in the chemical literature including the Chemical Abstracts) employing as starting material the compounds of formula (II) 
wherein the various substituents have the same meaning as in formula (I) and halo is a halogen atom, preferably bromine or iodine.
The compounds of formula (II) can be prepared by methods or processes similar to those described in International patent applications WO 87/03781, 93/06089, 94/21606, in European patent applications 295117, 403300, 385809, 500209, 679650, 285,893, and 780,381, U.S. Pat. Nos. 5,232,940, 5,236,938, 5,187,185, 5,223,525 and German Patent application 19511269 or by other methods known to the skilled addressee. The skilled addressee understands and is generally knowledgeable of Chemical Abstracts.
According to a first method of preparation of compounds of formula (I) from compounds of formula (II), a compound of formula (II) is caused to react with a boric acid or ester, preferably in presence of a coupling catalyst, so as to form a compound of formula (III) 
wherein the substituents have the same meaning as previously indicated, and B(OR30)2 represents a boric acid or ester group (R30 is preferably hydrogen, alkyl, or a divalent lower alkylene radical such that two R30O radicals may form a cyclic borate ester),
said compound (III) being, in a second step, caused to react with a compound of formula (VI) 
wherein R20 is bromine or iodine or Oxe2x80x94SO2CF3.
The first step of this first process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50xc2x0 C. and 150xc2x0 C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis (triphenylphosphine) palladium(O) or Pd2 (dibenzylidene acetone)3, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine. The boron derivative used as a reactant with the compound of formula (II) is preferably a cyclic diboron ester or acid of formula (R30O)2Bxe2x80x94B(OR30)2.
The second step of this first process is advantageously conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50xc2x0 C. and 150xc2x0 C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(O) or Pd2 (dibenzylidene acetone)3, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
According to another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (IV): 
wherein the substituents have the same meaning as previously indicated.
The process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50xc2x0 C. and 150xc2x0 C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(O) or Pd2 (dibenzylidene acetone)3, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react in the presence of a catalyst as described above, with a hexaalkylstannane [(alkyl or cycloalkyl)3Sn]2 so as to form a compound of formula (V): 
which in a second step is caused to react with a compound of formula (IV) in the presence of a coupling catalyst.
The first step of the process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether, at a temperature generally between 50xc2x0 C. and 150xc2x0 C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(O) or Pd2 (dibenzylidene acetone)3.
The second step of this second process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50xc2x0 C. and 150xc2x0 C.; as catalysts, organic derivatives of palladium such as Pd (P-phenyl3)4, Pd2 (dibenzylidene acetone)3, Pd (Oxe2x80x94COxe2x80x94CH3)2 may be cited.
According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (VII) 
preferably in the presence of a coupling catalyst as described above, and preferably in a solvent as described above, and preferably at a temperature from 50xc2x0 C. to 150xc2x0 C.
According to another method of preparation of a compound of formula (I), a compound of formula (VIII): 
is reacted in a step to form a pyrrole, imidazole, triazole, or pyrazole of formula (I). Such reactions are known and can be found in Katritzky, Rees, and Scriven, Comprehensive Heterocyclic Chemistry II, volumes 2.3.4 1996, Pergamon Press, London.
The invention is illustrated by the following examples, which are not considered as limiting the invention but are given to better enable use of it.